JP2015229303A - Window film and method of producing substrate with film stuck thereto - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a window film that prevents its function from deteriorating even after stuck to a substrate as a sticking object.SOLUTION: A window film has a dielectric multilayer film, wherein a dynamic friction coefficient under a wet condition between a reverse face of a substrate sticking face and an elastic body with a rubber hardness 60 is 0.2-0.5.

Description

  The present invention relates to a method for manufacturing a window film and a film pasting substrate.

  In recent years, many window films have been used which are bonded to windows of buildings and windows of vehicles. Such a window film has, for example, an infrared shielding ability that suppresses intrusion of infrared rays and prevents an excessive increase in building room temperature, thereby reducing the use of cooling and achieving energy saving. As a film having such optical shielding characteristics, a dielectric multilayer film in which layers having different refractive indexes are laminated is known. The dielectric multilayer film has an advantage that the spectral reflectance can be freely set by utilizing interference of reflected light from the boundary between layers.

  As a method for constructing the window film, a so-called water pasting method is widely used because re-stretching and re-positioning are easy. The general construction method of the water sticking method is to spray the water or surfactant liquid on the glass surface to which the film is to be attached to make it wet, and then the construction worker applies the pressure with a rubber member such as a spatula while the film is applied. A window film is bonded to the window glass by extruding moisture between the glass surface and the glass surface.

  Since window film is used by being affixed to building windows and vehicle components, it is not only long-term weather resistant but also has an initial scratch resistance that does not cause scratches when affixed with rubber members as described above. Sex is also required. Therefore, generally, a hard coat layer or an antifouling layer formed of an ultraviolet curable resin or a thermosetting resin for the purpose of surface protection is formed on the film surface (see, for example, Patent Document 1).

JP 2011-183742 A

  However, in the window film having a conventional dielectric multilayer film, there is a problem that when the film is bonded to the window, the function inherent to the film (for example, infrared reflection characteristics) cannot be sufficiently exhibited.

  Therefore, an object of the present invention is to provide a window film in which the deterioration of the function of the window film is suppressed even after being bonded to a substrate that is an object to be bonded.

  Another object of the present invention is to provide a method for producing a film pasting substrate in which the functions inherent to the window film are sufficiently exhibited.

  The present invention has a dielectric multilayer film, and has a wet dynamic friction coefficient of 0.2 to 0.5 between the reverse surface of the substrate bonding surface and the elastic body having a rubber hardness of 60. Related to film. The present invention also includes a step of wetting the substrate with an aqueous medium, and a step of disposing the window film on the substrate and pressing the film surface opposite to the substrate to remove the aqueous medium on the substrate. The present invention relates to a method for producing a film pasting substrate.

  According to the present invention, since the outermost surface of the window film on the opposite side of the substrate bonding surface has a wet dynamic friction coefficient of 0.2 to 0.5 with an elastic body having a rubber hardness of 60, the window glass Even after pasting, the function inherent to the window film can be maintained.

It is a cross-sectional schematic diagram of the window film which shows one Embodiment of this invention.

  One embodiment of the present invention has a dielectric multilayer film, and has a wet dynamic friction coefficient of 0.2 to 0.5 between the reverse surface of the substrate bonding surface and the elastic body having a rubber hardness of 60. It is a window film.

  FIG. 1 is a window film 10 showing an embodiment of the present invention. The window film 10 has the outermost layer 11, the dielectric multilayer film 12, the base material 13, and the adhesion layer 14 in order. The surface on the adhesive layer 14 side is the substrate bonding surface B, and the surface on the outermost layer 11 side is the reverse surface A of the substrate bonding surface. In the present invention, the wet dynamic friction coefficient of the reverse surface A of the substrate bonding surface and the elastic body having a rubber hardness of 60 is 0.2 to 0.5.

  As described above, the present inventor has found a phenomenon that the film function is lowered after bonding a substrate such as glass in a window film having a dielectric multilayer film. As a function of the window film, attention has been focused on improving the performance of the film itself, but little has been studied from the viewpoint of whether the function of the dielectric multilayer film can be maintained after being bonded to the glass substrate.

  According to the said embodiment, the function which a film originally has is maintained even after bonding a film to a base | substrate. The mechanism that this embodiment has such an effect is considered as follows. In the construction of a window film, the film is pressed with a rubber member in a wet state using water or a surfactant solution, and such pressing causes interface peeling between the respective layers of the dielectric multilayer film. When the wet dynamic friction coefficient with the rubber member is 0.5 or less, the bonding stress during construction on the dielectric multilayer film is reduced, and the occurrence of interface peeling of the dielectric multilayer film is eliminated or reduced. Conceivable. Also, when the wet friction coefficient with the rubber member exceeds 0.5, when the film is pressed with the rubber member in a wet state, a load is applied to the minute irregularities such as glass or glass, and cracks or defects are found in the film. Is likely to occur and increase. The cracks and defects generated in such a film are eroded by water and surfactant applied during construction, and the film is easily peeled off. In addition, when cracks or defects occur in the film, local rainbow unevenness is likely to occur due to the surfactant remaining in the scratches or the shape change in the film. Furthermore, in the long term, water will infiltrate into the fine irregularities due to repeated condensation and the like, and the irregularities will easily expand. For this reason, when the film is bonded to the substrate, it is considered that the function inherent to the film is lowered. On the other hand, when the wet friction coefficient with the rubber member is 0.5 or less, the bonding stress during construction on the dielectric multilayer film is reduced, and cracks / defects in the film are less likely to occur. Intrusion of water and surfactant into the inside is suppressed. As a result, it is considered that the film function is maintained even after the substrate is bonded. In addition, when the wet friction coefficient with the rubber member is less than 0.2, the rubber member and the film slip, so that the aqueous medium existing between the base and the film does not start well, and the remaining water and interface The activator is thought to reduce the film function after substrate bonding. On the other hand, when the wet friction coefficient with the rubber member is 0.2 or more, the aqueous medium between the film and the substrate can be almost removed, and the film function is maintained even after the substrate is bonded. It is considered a thing. In addition, this invention is not limited at all by the said mechanism.

[Window film]
The window film has at least a dielectric multilayer film, and the reverse surface of the substrate bonding surface has a wet friction coefficient of 0.2 to 0.5 with respect to an elastic body having a rubber hardness of 60.

  When the wet dynamic friction coefficient for an elastic body having a rubber hardness of 60 on the reverse side of the substrate bonding surface is less than 0.2 or more than 0.5, the film had before bonding after substrate bonding. Function declines.

  Further, when the wet friction coefficient is 0.2 to 0.5, even if dirt is attached, the dirt can be easily removed even by a weak external force such as rain, and the antifouling property is highly effective.

  The wet dynamic friction coefficient for the elastic body having a rubber hardness of 60 on the opposite side of the substrate bonding surface is 0.2 to 0.4 because the function of the film can be further maintained even after the substrate bonding. It is preferable that it is 0.3-0.4.

  Here, the elastic body having a rubber hardness of 60 is preferably any of natural rubber, silicon rubber, fluorine rubber, and urethane rubber, and more preferably made of urethane rubber. The rubber hardness is measured in accordance with JIS K6253-3: 2012 type A (Shore A), and a 20 mm × 20 mm 6000 μm thick test piece is measured in an environment of 23 ° C. and 55% RH. Adopts a value using a durometer GS-719N.

  The measurement of the coefficient of dynamic friction when wet was performed by dropping 0.5 ml of water on a 35 mm × 100 mm test piece, and then allowing the test piece to stand in an environment of 23 ° C. and 55% RH for 24 hours. To do.

  The method for measuring the dynamic friction coefficient conforms to JIS K7125: 1999 (ISO8295: 1995), and the other material described in JIS K7125 is a rubber elastic body having a rubber hardness of 60. The number of tests is three, and the average value is adopted. The load on the sliding piece is 200 g ± 2 g, and the speed is 100 / min. The test surface is the opposite surface of the substrate bonding surface.

  The total film thickness of the window film is preferably 10 μm to 300 μm, more preferably 20 μm to 250 μm. If it is this range, it will become a film excellent in transparency also in long-term use.

[Outermost layer]
The structure of the outermost layer (hereinafter also simply referred to as the outermost layer) having the opposite surface of the substrate bonding surface is particularly limited as long as the wet dynamic friction coefficient with respect to an elastic body having a rubber hardness of 60 satisfies 0.2 to 0.5. It is not a thing.

  Since the surface lubricity is improved, the wet surface dynamic friction coefficient of the outermost surface is easily adjusted to 0.2 to 0.5, and the protective property of the outermost layer is also improved. It is preferable that (1) contains a wax, (2) contains a silicone compound and a fluorine compound, and (3) contains at least one of (1) to (3) containing a fluorine-containing silicone.

  Each component of (1) to (3) may be used alone or in combination of two or more. Moreover, you may combine each form of (1), (2), (3).

(1) Wax When wax is contained, the wet friction coefficient on the outermost surface can be adjusted to 0.2 to 0.5 by appropriately selecting the wax content, wax type, and the like.

  Examples of the wax include petroleum wax, natural (plant-derived or animal-derived) wax, and the like.

  Petroleum waxes are paraffin waxes (hydrocarbons with high crystallinity separated and extracted from the portion of crude oil distilled under reduced pressure, and are mainly composed of linear hydrocarbons (normal paraffins) with a high melting point. Many are about 40 ° C to 70 ° C.), Microcrystalline wax (mainly wax extracted from the vacuum distillation residue oil portion of crude oil, and the constituent hydrocarbon is branched hydrocarbon (isoparaffin) or saturated cyclic carbonization The amount of hydrogen (cycloparaffin) is large, and thus crystals are smaller than that of paraffin wax, the molecular weight is large, and the melting point is as high as about 60 ° C. to 90 ° C.).

  Examples of natural waxes include carnauba wax, wood wax, rice bran wax (rice wax), candelilla wax, bees wax, wool wax, sperm wax, shellac wax, and chinese wax. Wax) and the like.

  Of the various waxes described above, carnauba wax, wood wax, rice bran wax (rice wax), and candelilla wax are preferred because the friction coefficient of the outermost layer is easily controlled and the surface protection is high.

  The said wax may be used individually by 1 type, and may be used together 2 or more types.

  When the outermost layer contains wax, the content of the wax is appropriately set so that the wet friction coefficient is 0.2 to 0.5, but 0.01% with respect to 100% by mass of the outermost layer solid content. It is preferable that it is -0.5 mass%, and it is more preferable that it is 0.01-0.3 mass%.

  The wax is preferably used in combination with a resin, and is preferably used in combination with a cured resin described below.

(2) Silicone compound and fluorine compound When the silicone compound and fluorine compound are contained, wetting the outermost surface by appropriately selecting the content, content ratio, compound type, etc. of the silicone compound and fluorine compound. The hourly friction coefficient can be adjusted to 0.2 to 0.5.

  As the fluorine-based compound, an organic compound containing fluorine (preferably having 1 to 30 carbon atoms) and a polymer derived from the organic compound are preferable. Specifically, the carbon number is preferably 1 to 24, and more preferable. 1 to 12, more preferably 1 to 8 fluorine-containing alcohol; (meth) acrylic acid fluoroalkyl ester (the number of carbon atoms in the fluoroalkyl moiety is preferably 1 to 24, more preferably 1 to 12, Preferably 1 to 8); a fluorine-containing olefin having 1 to 24 carbon atoms, more preferably 1 to 12 carbon atoms, more preferably 1 to 8 carbon atoms; more preferably 1 to 24 carbon atoms. Is preferably a fluorine-containing alkylphosphonic acid having 1 to 12, more preferably 1 to 8; a fluorine-containing diol having 6 to 30 carbon atoms (preferably a fluorine-containing bisphenol). Since the (meth) acrylic acid fluoroalkyl ester and the fluorine-containing olefin have a polymerizable functional group, a polymer derived from these compounds may be produced during the curing reaction or over time. Accordingly, the fluorine-based compound also includes a polymer derived from a compound having these polymerizable responsive groups.

  In the present specification, (meth) acryl is a general term for acrylic and methacrylic.

  Examples of the fluorinated alcohol include trifluoroethanol, 2,2,3,3,3-pentafluoro-1-propanol, 2- (perfluorobutyl) ethanol, 2- (perfluorohexyl) ethanol, and 2- (perfluoro Octyl) ethanol, 2- (perfluorodecyl) ethanol, 2- (perfluoro-3-methylbutyl) ethanol, 1H, 1H, 3H-tetrafluoro-1-propanol, 1H, 1H, 5H-octafluoro-1-pen Tanol, 1H, 1H, 7H-dodecafluoro-1-heptanol, 1H, 1H, 9H-hexadecafluoro-1-nonanol, 2H-hexafluoro-2-propanol, 1H, 1H, 3H-hexafluoro-2-butanol Etc.

  (Meth) acrylic acid fluoroalkyl esters include 2,2,2-trifluoroethyl (meth) acrylate, 1,1,1,3,3,3-hexafluoro-2-propyl (meth) acrylate, perfluoro Ethylmethyl (meth) acrylate, perfluoropropylmethyl (meth) acrylate, perfluorobutylmethyl (meth) acrylate, perfluoropentylmethyl (meth) acrylate, perfluorohexylmethyl (meth) acrylate, perfluoroheptylmethyl (meth) Acrylate, perfluorooctylmethyl (meth) acrylate, perfluorononylmethyl (meth) acrylate, perfluorodecylmethyl (meth) acrylate, perfluoroundecylmethyl (meth) acrylate, perfluoride Silmethyl (meth) acrylate, perfluorotridecylmethyl (meth) acrylate, perfluorotetradecylmethyl (meth) acrylate, 2- (trifluoromethyl) ethyl (meth) acrylate, 2- (perfluoroethyl) ethyl (meth) Acrylate, 2- (perfluoropropyl) ethyl (meth) acrylate, 2- (perfluorobutyl) ethyl (meth) acrylate, 2- (perfluoropentyl) ethyl (meth) acrylate, 2- (perfluorohexyl) ethyl ( (Meth) acrylate, 2- (perfluoroheptyl) ethyl (meth) acrylate, 2- (perfluorooctyl) ethyl (meth) acrylate, 2- (perfluorononyl) ethyl (meth) acrylate, 2- (perfluorodecyl) ethyl( Acrylate), 2- (perfluoroundecyl) ethyl (meth) acrylate, 2- (perfluorododecyl) ethyl (meth) acrylate, 2- (perfluorotridecyl) ethyl (meth) acrylate, 2- (perfluoro Tetradecyl) ethyl (meth) acrylate and the like.

  Examples of the fluorine-containing olefin include perfluorohexylethylene, perfluorooctylethylene, and perfluorodecylethylene.

  Examples of the fluorine-containing alkylphosphonic acid include 2- (perfluorohexyl) ethylphosphonic acid.

  Examples of the fluorine-containing diol include 2,2-bis (4-hydroxyphenyl) hexafluoropropane, 2,2-bis (4-hydroxy-3-methylphenyl) hexafluoropropane, and 2,2-bis (3-ethyl- 4-hydroxyphenyl) hexafluoropropane, 2,2-bis (4-hydroxy-3,5-dimethylphenyl) hexafluoropropane, 2,2-bis (3-fluoro-4-hydroxyphenyl) hexafluoropropane, 2, , 2-bis (3-bromo-4-hydroxyphenyl) hexafluoropropane, 2,2-bis (3,5-dibromo-4-hydroxyphenyl) hexafluoropropane, and the like.

  Among the above-mentioned various fluorine-based compounds, the friction coefficient of the outermost layer is easily controlled, and the surface protection is high. Therefore, heavy weight derived from (meth) acrylic acid fluoroalkyl esters and (meth) acrylic acid fluoroalkyl esters Coalescence is preferred.

  The said fluorine-type compound may be used individually by 1 type, and may be used together 2 or more types.

  When the outermost layer contains a fluorine compound, the content of the fluorine compound is appropriately set so that the wet friction coefficient is 0.2 to 0.5, but with respect to the outermost layer solid content of 100% by mass. 0.05 to 5 mass% is preferable, and 0.1 to 3 mass% is more preferable.

  The fluorine compound is preferably used in combination with a silicone compound from the viewpoint of compatibility. A silicone compound is a compound having a main skeleton formed by a siloxane bond.

  The mass ratio in the outermost layer of the silicone compound and the fluorine compound is not particularly limited, but the silicone compound: fluorine compound = 1: 0.005 because the effects of the present invention are further obtained. It is preferable that it is -0.5, and it is more preferable that it is 0.005-0.1.

  Examples of the silicone compound include silicone resins such as resins composed of partially hydrolyzed oligomers of alkoxysilane compounds; (meth) acryl-modified silicone compounds.

The alkoxysilane compound in the resin comprising the partially hydrolyzed oligomer of the alkoxysilane compound is represented by the general formula of R _m Si (OR ′) _n , and R and R ′ are alkyls having 1 to 10 carbon atoms. Represents a group, and m and n are integers satisfying the relationship of m + n = 4.

  Specific examples of the alkoxysilane compound include tetramethoxysilane, tetraethoxysilane, tetra-iso-propoxysilane, tetra-n-popropoxysilane, tetra-n-butoxysilane, tetra-sec-butoxysilane, and tetra-tert-. Butoxysilane, terapentaethoxysilane, tetrapenta-iso-propoxysilane, tetrapenta-n-propoxysilane, tetrapenta-n-butoxysilane, tetrapenta-sec-butoxysilane, tetrapenta-tert-butoxysilane, methyltriethoxysilane, methyltriethoxysilane Propoxysilane, methyltributoxysilane, dimethyldimethoxysilane, dimethyldiethoxysilane, dimethylethoxysilane, dimethylmethoxysilane, dimethylpropoxysilane Dimethyl-butoxy silane, dimethyl dimethoxy silane, dimethyl diethoxy silane, hexyl trimethoxy silane and the like.

  For example, after obtaining a partially hydrolyzed oligomer as described in JP 2012-232538 A [0129], a curing catalyst such as acetic acid or maleic acid is added to these alkoxysilane compounds, and alcohol, A silicone resin is obtained by dissolving in a glycol ether organic solvent and then polycondensing with heat.

  Since a film obtained from such a silicone resin generally has a hard coat property, it is also referred to as a polyorganosiloxane hard coat.

  Commercially available products can be used as the silicone resin, such as Sarkote series NP-720, 730, Sarkote BP-16N (manufactured by Doken), SR2441 (Toray Dow Corning), KP-86 (Shin-Etsu Silicon) Perma-New (registered trademark) 6000 (California Hardcoating Company), Tosgard 510 (silicone resin) (Momentive Performance Materials), and the like can be used.

  “(Meth) acrylic modified silicone compound” means that a (meth) acrylic group is introduced at any position (preferably terminal (one terminal or both terminals), more preferably both terminals) such as the side chain or terminal of the silicone skeleton. As this compound itself, a conventionally known compound can be appropriately used. Specific examples of the (meth) acryl-modified silicone compound include TEGO Rad2010 / Rad2011 (manufactured by EVONIC), SQ100 / SQ200 (manufactured by Tokushiki), CN990 / CN9800 (manufactured by Sartomer), EBECRYL350 (manufactured by Daicel Ornex), X-22-2445 / X-22-1602 (both terminal acrylate silicone), X-22-164 / X-22-164AS / X-22-164A / X-22-164B / X-22-164C / X- 22-164E (both ends methacrylate silicone), X-22-174ASX / X-22-174BX / KF-2012 / X-22-2426 / X-22-2475 (one end methacrylate silicone) (Shin-Etsu Chemical Co., Ltd.) Manufactured by), BYK UV-3500 / BY And the like UV-3570 (manufactured by BYK Japan KK). Further, (meth) acryloxypropyl-terminated polydimethylsiloxane, [(meth) acryloxypropyl] methylsiloxane, a copolymer of [(meth) acryloxypropyl] methylsiloxane and dimethylsiloxane, and the like can also be used. In addition, those in which a methyl group is introduced at the terminal of the (meth) acryl group of these compounds can also be used. The number of functional groups in one molecule is preferably 2 or more, but one having 1 functional group may be used. The functional group equivalent is preferably in the range of 100 to 1000.

  The said silicone type compound may be used individually by 1 type, and may be used together 2 or more types.

  The content of the silicone compound in the case where the outermost layer contains a silicone compound is appropriately set so that the wet friction coefficient is 0.2 to 0.5, but with respect to the outermost layer solid content of 100% by mass. 1 to 50% by mass, more preferably 5 to 40% by mass.

(3) Fluorine-containing silicone Fluorine-containing silicone is obtained by introducing fluorine bonds (fluorine-containing substituents) into polysiloxane composed of siloxane bonds. If it is fluorine-containing silicone, the form of oil, resin, etc. is not limited, but considering the hard coat properties, it is preferably a silicone resin.

  The fluorine-containing substituent is not particularly limited, and examples thereof include perfluoromethylethyl group, perfluoroethylmethyl group, perfluoroethylethyl group, perfluoropropylethyl group, perfluorobutylethyl group, perfluoro -X-Rf group such as a pentylethyl group, a perfluoropentylpropyl group, a perfluorohexylethyl group (wherein X is a divalent organic group (preferably having a carbon number) which may have an oxygen atom or a nitrogen atom) An organic group having 1 to 12 carbon atoms, more preferably an alkylene group having 1 to 12 carbon atoms), and Rf represents a perfluoroalkyl group (preferably 1 to 10 carbon atoms).

  The bonding position of the fluorine-containing substituent is not particularly limited, and may be present at both ends and one end of the main chain, or may be present at the side chain, and the side chain and end (both ends, one end). ) May have an introduced substituent.

  The introduction amount of the fluorine-containing substituent in the fluorine-containing silicone is appropriately set so that the wet friction coefficient of the outermost layer is 0.2 to 0.5, but is 0 for 100 parts by weight of the fluorine-containing silicone. The amount is preferably 0.01 to 5 parts by weight, more preferably 0.05 to 5 parts by weight.

  As the fluorine-containing silicone, a fluorine-containing organopolysiloxane in which a part of alkyl groups of an alkyl group-containing silicone such as organopolysiloxane or acrylic-modified organopolysiloxane is substituted with the above-mentioned fluorine-containing substituent, JP-A-2011-184527 Examples include fluorine-containing silicone polymers having the three-dimensional crosslinked structure described above, fluorine-containing organopolysiloxanes described in JP-A No. 2001-172461, amino group-containing fluorine-containing organopolysiloxanes described in JP-A No. 7-18079, and the like. Can do.

  Commercially available products can also be used as the fluorine-containing silicone, and commercially available products include FL-5, FL-100-100cs, FL-100-450cs, FL-100-1000cs, FL-100-10000cs, X-22-821. X-22-822 (manufactured by Shin-Etsu Chemical Co., Ltd.), FS1265 (manufactured by Dow Corning Toray) and the like.

  The production method of the fluorine-containing organopolysiloxane is not particularly limited. For example, after reacting a fluorine-containing compound (for example, trifluoropropene) with silanes, obtaining a cyclic monomer by hydrolysis and cracking, the method is opened. It can be obtained by ring polymerization.

Alternatively, the fluorine-containing silicone is an alkyl group-containing silicone and an organic compound containing fluorine described in the column of the fluorine-based compound (specifically, the number of carbon atoms is preferably 1 to 24, more preferably 1 to 24, 12, more preferably 1 to 8 fluorinated alcohol; (meth) acrylic acid fluoroalkyl ester (the fluoroalkyl moiety preferably has 1 to 24 carbon atoms, more preferably 1 to 12, more preferably 1) -8); a fluorinated olefin having 1 to 24 carbon atoms, more preferably 1 to 12, more preferably 1 to 8 carbon atoms; preferably 1 to 24 carbon atoms, more preferably 1 to 8 carbon atoms. 12 and more preferably a fluorine-containing alkylphosphonic acid having 1 to 8; a fluorine-containing diol (preferably a fluorine-containing bisphenol) having 6 to 30 carbon atoms, and the like. It can be. The reaction conditions at this time can be appropriately set in consideration of the silicone species and the organic compound species containing fluorine. In the reaction, a reaction catalyst such as LiCl, Me ₂ Zn, Pr ₂ Zn, or Bu ₂ Zn may be used.

  Generally, the outermost layer of the window film is required to have hard coat properties and antifouling properties for the purpose of surface protection. For this reason, it is preferable that the outermost layer of the window film contains a cured resin in order to impart hard coat properties and antifouling properties.

  Examples of the curable resin include a thermosetting resin and an active energy ray curable resin, but an active energy ray curable resin is preferable because of easy molding.

  The active energy ray-curable resin is a resin that is cured through a crosslinking reaction or the like by irradiation with active energy rays such as ultraviolet rays or electron beams. As the active energy ray curable resin, a component containing a monomer having an ethylenically unsaturated double bond is preferably used, and the active energy ray hard coat layer is cured by irradiation with an active energy ray such as an ultraviolet ray or an electron beam. Is formed. Typical examples of the active energy ray curable resin include an ultraviolet curable resin, an electron beam curable resin, and the like, but an ultraviolet curable resin that is cured by ultraviolet irradiation is preferable.

  Specific examples of the cured resin include acrylic resins, urethane resins, melamine resins, epoxy resins, organic silicate compounds, and silicone resins.

  Such cured resins can be used singly or in combination of two or more. Moreover, a commercial product may be used for the cured resin, and a synthetic product may be used.

  In particular, an acrylic resin is preferable in terms of hardness and durability, and an active energy ray-curable acrylic resin is more preferable.

  The acrylic resin is preferably obtained by curing a composition containing a polyfunctional acrylate, an acrylic oligomer, or a reactive diluent as a polymerization curing component. In addition, you may use what contains a photoinitiator, a photosensitizer, a thermal-polymerization initiator, a modifier, etc. as needed.

  Acrylic oligomers include polyester acrylates, urethane acrylates, epoxy acrylates, polyether acrylates, etc., including those in which a reactive acrylic group is bonded to an acrylic resin skeleton, and rigid materials such as melamine and isocyanuric acid. A structure in which an acrylic group is bonded to a simple skeleton can also be used.

  In addition, the reactive diluent has a function of a solvent in the coating process as a medium of the coating agent, and has a group that itself reacts with a monofunctional or polyfunctional acrylic oligomer. It becomes a copolymerization component.

  As these ultraviolet curable resins, commercially available products may be used. Specifically, Beamset (registered trademark) Beamset 575, 777, 575CB, 575CL, 575CN, 907, 1200, 1402, 1461, 1702 ( Arakawa Chemical Industries, Ltd.); Sartomer SR295, SR399 (Sartomer); Acryt 0403KA and other Acryt series (Taisei Fine Chemicals); Diabeam (registered trademark) series (Mitsubishi Rayon; Denacol (registered trademark) series (Nagase Sangyo Co., Ltd.) NK ester series (Shin Nakamura Chemical Co., Ltd.), UNIDIC (registered trademark) series (DIC Corporation), Aronix (registered trademark) series (Toagosei Co., Ltd.); Blemmer (registered trademark) series (Manufactured by NOF Corporation); KAYARAD (registered trademark) Series (manufactured by Nippon Kayaku Co., Ltd.); Light Ester Series, LIGHT ACRYLATE Series (manufactured by Kyoeisha Chemical Co., Ltd.), and the like.

  The blending amount of the active energy ray-curable acrylic resin in the outermost layer is preferably 40 to 99.99% by mass with respect to a total of 100% by mass (solid content conversion) of the outermost layer.

The outermost layer may contain inorganic nanoparticles for the purpose of providing an infrared shielding function and improving mechanical strength. Here, the nano fine particles refer to particles having an average (primary) particle size of less than 1000 nm, more preferably those having an average particle size in the range of 1 to 500 nm, and even more preferably those in the range of 1 to 100 nm. The particle diameter means the maximum distance among the distances between any two points on the outline of the particle (observation surface) observed using an observation means such as a transmission electron microscope. In addition, the (primary) average particle diameter referred to in this specification is a method of observing the particles themselves using a laser diffraction scattering method, a dynamic light scattering method, or an electron microscope, or appears on the cross section or surface of the refractive index layer. It is a value obtained by measuring the particle diameter of 1,000 arbitrary particles by a method of observing the observed particle image with an electron microscope, and calculating the average. Examples of such inorganic nanoparticles include zinc oxide, silicon oxide, cesium oxide, alumina, zirconia, titanium oxide or cerium oxide, and these compounds doped with other metals (antimony-doped tin oxide (ATO) or indium oxide). Tin (ITO), antimony doped zinc oxide, indium doped zinc oxide (indium zinc composite oxide: IZO), gallium doped zinc oxide (gallium zinc composite oxide: GZO), aluminum doped zinc oxide (aluminum zinc composite oxide: AZO) ), Tungsten-doped cesium oxide (tungsten cesium composite oxide), lanthanum boride, etc.), and mixtures thereof. In addition, Cd / Se, GaN, Y ₂ O ₃ , Au, Ag, and Cu nanoparticles can also be used.

  It is preferable that the compounding quantity in the outermost layer of inorganic nanoparticle is 1-80 mass% with respect to the whole solid content.

  Other materials that can be used for the outermost layer include thermosetting inorganic materials, aqueous colloidal silica-containing acrylic resins (Japanese Patent Laid-Open No. 2005-66824), and polyurethane resin compositions (Japanese Patent Laid-Open No. 2005-110918). ), A resin film using an aqueous silicone compound as a binder (Japanese Patent Laid-Open No. 2004-142161), a photocatalytic oxide-containing silica film such as titanium oxide or alumina, a photocatalytic film such as titanium oxide or niobium oxide having a high aspect ratio ( JP2009-62216), photocatalyst-containing fluororesin coating (Pierex Technologies), organic / inorganic polysilazane film, organic / inorganic polysilazane to hydrophilization accelerator (AZ Electronics), acrylic surfactant, silicon-based interface Activator, lanthanum boride, nickel Le complex-based compounds, immonium dyes, phthalocyanine dyes, infrared absorbing agents such as aminium compounds, dyes, and a pigment.

  The thickness of the outermost layer is appropriately set in consideration of hard coat properties, antifouling properties, and flex resistance of the film, but is preferably 0.1 to 20 μm, more preferably 1 to 15 μm, and more preferably 3 to 10 μm. More preferred.

  A method for producing the outermost layer is not particularly limited, but a coating solution containing a material and a solvent constituting the outermost layer is applied by a wet method such as a spin coating method, a spray method, a blade coating method, a dip method, or a gravure printing method. Examples thereof include a coating method or a dry coating method such as a vapor deposition method.

  When the wet coating method is used, the amount of the solvent in the coating solution for forming the outermost layer is appropriately set in such an amount that the material constituting the outermost layer can be dissolved and dispersed. About 80% by mass.

  After applying the coating liquid to form a coating film, it is preferable to dry the film to remove the solvent.

  After drying, the outermost layer can be obtained by curing the coating film by irradiation and / or heating with active energy rays such as visible rays, infrared rays, ultraviolet rays, X rays, α rays, β rays, γ rays, and electron beams. it can.

[Dielectric multilayer film]
The dielectric multilayer film is a laminate of layers having different refractive indexes, but is preferably a laminate in which high refractive index layers and low refractive index layers are alternately laminated.

  The terms “high refractive index layer” and “low refractive index layer” are obtained by comparing the refractive index difference between two adjacent layers with the higher refractive index layer as the higher refractive index layer and the lower refractive index layer. This means that the refractive index layer is a low refractive index layer. Therefore, the terms “high refractive index layer” and “low refractive index layer” mean that each refractive index layer has the same refractive index when attention is paid to two adjacent refractive index layers. All forms other than the forms having the above are included.

  Since reflection at the interface between adjacent layers depends on the refractive index ratio between the layers, the larger the refractive index ratio, the higher the reflectance. In addition, when the optical path difference between the reflected light on the surface of the layer and the reflected light on the bottom of the layer is a relationship expressed by n · d = wavelength / 4 when viewed as a single layer film, the reflected light is controlled to be strengthened by the phase difference. And reflectivity can be increased. Here, n is the refractive index, d is the physical film thickness of the layer, and n · d is the optical film thickness. By using this optical path difference, reflection can be controlled. By utilizing this relationship, the refractive index and film thickness of each layer are controlled to control the reflection of ultraviolet light, visible light, and near infrared light. That is, the reflectance in a specific wavelength region can be increased by the refractive index of each layer, the film thickness of each layer, and the way of stacking each layer.

  Therefore, the functional film having a dielectric multilayer film is preferably an optical reflection film having optical reflection characteristics such as infrared shielding ability and ultraviolet shielding ability.

  The thickness of the dielectric multilayer film is appropriately designed so that the dielectric multilayer film to be used and a desired function are exhibited, but is usually about 1 to 100 μm.

  As the material for forming the dielectric multilayer film, conventionally known materials can be used, and examples thereof include metal oxide materials, polymers, other additives, and combinations thereof.

Examples of the metal oxide material include TiO ₂ , ZrO ₂ , Ta ₂ O _{5 and the} like as high refractive index materials, SiO ₂ and MgF ₂ as low refractive index materials, and Al ₂ as medium refractive index material. O ₃ etc. are mentioned. These metal oxide materials can be formed by a dry film forming method such as vapor deposition or sputtering.

  The dielectric multilayer film may be a dielectric multilayer film by adjusting the refractive index difference of each layer using a polymer. The polymer contained in the dielectric multilayer film is not particularly limited as long as it is a polymer that can form the dielectric multilayer film. However, since the refractive index of each refractive index layer can be easily controlled, the dielectric multilayer film is made of polyester. It is preferable to contain at least one of a system polymer and a water-soluble polymer. Moreover, since the adhesiveness between each layer can be improved and the effects of the present invention can be obtained more remarkably, the dielectric multilayer film more preferably contains a water-soluble polymer.

  The water-soluble polymer suitably used as the polymer can be applied in an aqueous system without using an organic solvent, and therefore has a low environmental load and high flexibility, so that the durability of the film during bending is improved.

  Examples of the water-soluble polymer include polyvinyl alcohols, polyvinyl pyrrolidones, polyacrylic acid, acrylic acid-acrylonitrile copolymer, potassium acrylate-acrylonitrile copolymer, vinyl acetate-acrylic ester copolymer, or Acrylic resins such as acrylic acid-acrylic acid ester copolymer, styrene-acrylic acid copolymer, styrene-methacrylic acid copolymer, styrene-methacrylic acid-acrylic acid ester copolymer, styrene-α-methylstyrene- Styrene acrylic acid resin such as acrylic acid copolymer or styrene-α-methylstyrene-acrylic acid-acrylic acid ester copolymer, styrene-sodium styrenesulfonate copolymer, styrene-2-hydroxyethyl acrylate copolymer Styrene 2-hydroxyethyl acrylate-potassium styrene sulfonate copolymer, styrene-maleic acid copolymer, styrene-maleic anhydride copolymer, vinyl naphthalene-acrylic acid copolymer, vinyl naphthalene-maleic acid copolymer, acetic acid Synthetic water-soluble polymers such as vinyl-acetic acid copolymers, vinyl acetate-crotonic acid copolymers, vinyl acetate-acrylic acid copolymers, and other vinyl acetate copolymers and their salts; gelatin, thickening And natural water-soluble polymers such as polysaccharides. Among these, particularly preferred examples include polyvinyl alcohol, polyvinylpyrrolidones and copolymers containing them, gelatin, thickening polysaccharides (particularly celluloses) from the viewpoint of handling during production and film flexibility. Is mentioned. These water-soluble polymers may be used alone or in combination of two or more.

  Polyvinyl alcohol includes modified polyvinyl alcohol in addition to ordinary polyvinyl alcohol obtained by hydrolyzing polyvinyl acetate. Examples of the modified polyvinyl alcohol include cation-modified polyvinyl alcohol, anion-modified polyvinyl alcohol, nonion-modified polyvinyl alcohol, and vinyl alcohol polymers.

  Specific examples of polyvinyl alcohol include those described in [0075] to [0079] of International Publication No. 2013-054912.

  Moreover, you may use the hardening | curing agent for hardening polyvinyl alcohol. As an applicable curing agent, for example, boric acid and its salt are preferable. Specific examples of the other curing agent include those described in [0091] to [0096] of International Publication No. 2013-054912.

  As the gelatin, in addition to lime-processed gelatin, acid-processed gelatin may be used, and further, a hydrolyzate of gelatin and an enzyme-decomposed product of gelatin can be used. Moreover, you may use the hardening agent as described in [0081]-[0082] of international publication 2013-054912.

  Examples of thickening polysaccharides include natural simple polysaccharides, natural complex polysaccharides, synthetic simple polysaccharides and synthetic complex polysaccharides that are generally known. Reference can be made to the encyclopedia (2nd edition), Tokyo Kagaku Doujin Publishing, “Food Industry”, Vol. 31 (1988), p.

  The said water-soluble polymer may be used individually by 1 type, and may be used together 2 or more types.

  The weight average molecular weight of the water-soluble polymer is preferably 1,000 or more and 200,000 or less. As the weight average molecular weight, a value (standard substance pullulan) using gel permeation chromatography (GPC) is adopted.

  When the dielectric multilayer film contains a water-soluble polymer, aqueous coating can be performed. Examples of a method for forming a dielectric multilayer film using a water-soluble polymer and an aqueous solvent include a sequential multilayer coating method; and a simultaneous multilayer coating method described in International Publication No. 2013-054912 [0144] to [0156]. Can be mentioned.

  As the polyester polymer, a polyester resin described in JP-T-2002-509279 can be used. Specifically, polyethylene naphthalate (PEN) and its isomers (for example, 2,6-, 1,4-, 1,5-, 2,7-, and 2,3-PEN), polyalkylene terephthalate ( For example, polyethylene terephthalate, polypropylene terephthalate, polybutylene terephthalate, and poly-1,4-cyclohexanedimethylene terephthalate), polyimide (eg, polyacrylimide), polyetherimide, atactic polystyrene, polycarbonate, polymethacrylate (eg, Polyisobutyl methacrylate, polypropyl methacrylate, polyethyl methacrylate, and polymethyl methacrylate), poly (meth) acrylates (eg, polybutyl acrylate and polymethyl acrylate), co- Limers (eg, copolymers of PEN (eg 2,6-, 1,4-, 1,5-, 2,7- and / or 2,3-naphthalenedicarboxylic acid or esters thereof; (a) terephthalate) Acid or ester thereof, (b) isophthalic acid or ester thereof, (c) phthalic acid or ester thereof, (d) alkylene glycol (eg, ethylene glycol, propylene glycol), (e) cycloalkylene glycol (eg, cyclohexanedimethanol) Diol), (f) alkanedicarboxylic acid, and / or (g) copolymer with cycloalkanedicarboxylic acid (eg, 1,4-, 1,2-cyclohexanedicarboxylic acid), polyalkylene terephthalate copolymer (eg, terephthalate) Acid or its ester (A) naphthalene dicarboxylic acid or ester thereof, (b) isophthalic acid or ester thereof, (c) phthalic acid or ester thereof, (d) alkylene glycol (for example, ethylene glycol, propylene glycol), (e) cycloalkane glycol ( (E.g., cyclohexanedimethanol), (f) alkanedicarboxylic acid, and / or (g) copolymer with cycloalkanedicarboxylic acid (e.g., cyclohexanedicarboxylic acid)), styrene copolymer (e.g., styrene-butadiene copolymer and styrene-acrylonitrile copolymer). , And a copolymer of 4,4′-dibenzoic acid and ethylene glycol).

  Furthermore, you may use the polymer of Unexamined-Japanese-Patent No. 2010-184493 as a polyester-type polymer. Specifically, a polyester (hereinafter referred to as polyester A) and a polyester (hereinafter referred to as polyester B) containing residues derived from at least three diols of ethylene glycol, spiroglycol and butylene glycol, Can be used. Polyester A is not particularly limited as long as it has a structure obtained by polycondensation of a dicarboxylic acid component and a diol component. The polyester B contains residues derived from at least three kinds of diols, ethylene glycol, spiroglycol and butylene glycol.

  The said polyester polymer may be used individually by 1 type, and may be used together 2 or more types.

  As described in US Pat. No. 6,049,419, the polyester-based polymer can form a dielectric multilayer film by melt extrusion and stretching of the polymer.

  In one embodiment, each refractive index layer material is melted at 100 to 400 ° C. to have a viscosity suitable for extrusion, and various additives are added as necessary, so that both polymers are alternately formed into two layers. Can be extruded by an extruder. Next, the extruded laminated film is cooled and solidified by a cooling drum to obtain a laminated body. Thereafter, the laminate is heated and then stretched in two directions to obtain a dielectric multilayer film. When extending | stretching in the direction orthogonal to a film conveyance direction or a film conveyance direction, it is preferable to extend | stretch by the magnification of 1.5-5.0 times, More preferably, it is the range of 2.0-4.0 times.

  Moreover, it can also heat-process subsequent to extending | stretching. The heat-processed film is usually cooled to Tg or less, and clip holding portions at both ends of the film are cut and wound. The means for cooling is not particularly limited, and can be performed by a conventionally known means. In particular, it is preferable to perform these treatments while sequentially cooling in a plurality of temperature ranges from the viewpoint of improving the dimensional stability of the film.

  The refractive index layer of the functional film obtained by polymer melt extrusion and stretching is preferably 10 to 5000 layers, more preferably 20 to 2000 layers.

  The dielectric multilayer film may contain metal oxide particles in addition to the polymer. The metal oxide particles may be contained in any of the films constituting the dielectric multilayer film. However, a preferable form is that at least the high refractive index layer includes metal oxide particles, and a more preferable form is a high refractive index. Both the layer and the low refractive index layer are in a form containing metal oxide particles.

  As the metal oxide particles, the metal constituting the metal oxide is Li, Na, Mg, Al, Si, K, Ca, Sc, Ti, V, Cr, Mn, Fe, Co, Ni, Cu, Zn, Rb, Sr, Y, Nb, Zr, Mo, Ag, Cd, In, Sn, Sb, Cs, Ba, La, Ta, Hf, W, Ir, Tl, Pb, Bi and a rare earth metal A metal oxide which is one kind or two or more kinds of metals can be used.

  The metal oxide particles preferably have an average particle size of 100 nm or less, 4 to 50 nm, or 4 to 30 nm in order of preference. Here, the average particle diameter refers to the primary average particle diameter. When the metal oxide particles are coated (for example, silica-attached titanium oxide), the average particle diameter of the metal oxide particles is the matrix (in the case of silica-attached titanium oxide). , Titanium oxide before treatment).

  The content of the metal oxide particles in each refractive index layer is preferably 20 to 90% by mass and more preferably 40 to 75% by mass with respect to the total mass of the refractive index layer.

  In the low refractive index layer, silicon dioxide (silica) is preferably used as the metal oxide particles, and acidic colloidal silica sol is particularly preferably used.

Examples of the metal oxide contained in the high refractive index layer include titanium oxide, zinc oxide, aluminum oxide (alumina), zirconium oxide, hafnium oxide, niobium oxide, tantalum oxide, magnesium oxide, barium oxide, indium oxide, and oxide. Examples include tin and lead oxide, and composite oxide particles such as lithium niobate, potassium niobate, lithium tantalate, and aluminum / magnesium oxide (MgAl ₂ O ₄ ), which are complex oxides composed of these oxides. In order to form a transparent, high refractive index layer having a higher refractive index, high refractive index metal oxide fine particles such as titanium and zirconia, that is, titanium oxide fine particles and zirconia fine particles are preferable. ) Titanium oxide fine particles are more preferable.

  Further, as the titanium oxide particles, those obtained by modifying the surface of an aqueous titanium oxide sol to stabilize the dispersion state, as described in International Publication No. 2013-054912, the titanium oxide particles are hydrated oxides containing silicon. The core-shell particles manufactured by a known method may be used.

[Base material]
The window film may have a base material.

  The substrate used is not particularly limited, but is preferably a resin substrate from the viewpoint of flexibility and the like, and may be transparent or opaque. For applications that are required to be transparent with visible light from the viewpoint of design, such as automotive applications, it is preferably transparent in the visible light region.

  As the resin substrate, for example, a polyolefin film (polyethylene, polypropylene, etc.), a polyester film (polyethylene terephthalate, polyethylene naphthalate, etc.), polyvinyl chloride, cellulose acetate, etc. can be used, and a polyester film is preferred.

  As thickness of a base material, it is preferable that it is 10-300 micrometers, and it is more preferable that it is 20-150 micrometers. Moreover, the base material may be a laminate of two or more, and in this case, the type may be the same or different.

  The resin base material can be manufactured by a conventionally known general method. The resin substrate may be an unstretched film, a stretched film stretched on one side, or a biaxially stretched film. A stretched film is preferable from the viewpoint of strength improvement and thermal expansion suppression. In particular, when used as a windshield of an automobile, a stretched film is more preferable.

[Adhesive layer]
An adhesive layer can be provided on the bonding surface of the window film with the substrate.

  The pressure-sensitive adhesive constituting the pressure-sensitive adhesive layer is not particularly limited, and examples thereof include acrylic pressure-sensitive adhesives, silicon-based pressure-sensitive adhesives, urethane-based pressure-sensitive adhesives, polyvinyl butyral pressure-sensitive adhesives, and ethylene-vinyl acetate pressure-sensitive adhesives. Can do.

  When the window film of the present invention is bonded to a window glass, it is preferable to use a so-called water bonding method in which water is sprayed onto the glass surface and the adhesive layer of the window film is combined with the wet glass surface. And this water sticking method is used suitably from viewpoints, such as re-stretching and re-positioning. For this reason, an acrylic pressure-sensitive adhesive that has a weak adhesive force in the presence of water is preferably used.

  The acrylic pressure-sensitive adhesive used may be either solvent-based or emulsion-based, but is preferably a solvent-based pressure-sensitive adhesive because it is easy to increase the adhesive strength and the like, and among them, those obtained by solution polymerization are preferable. As a raw material when producing such a solvent-based acrylic pressure-sensitive adhesive by solution polymerization, for example, as a main monomer serving as a skeleton, an acrylic ester such as ethyl acrylate, butyl acrylate, 2-ethylhexyl acrylate, acryl acrylate, As a comonomer to improve cohesive strength, vinyl acetate, acrylonitrile, styrene, methyl methacrylate, etc., to further promote crosslinking, to give stable adhesive strength, and to maintain a certain level of adhesive strength even in the presence of water Examples of the functional group-containing monomer include methacrylic acid, acrylic acid, itaconic acid, hydroxyethyl methacrylate, and glycidyl methacrylate. Since the adhesive layer of the laminated film requires a particularly high tack as the main polymer, those having a low glass transition temperature (Tg) such as butyl acrylate are particularly useful.

  This adhesive layer contains additives such as stabilizers, surfactants, UV absorbers, flame retardants, antistatic agents, antioxidants, thermal stabilizers, lubricants, fillers, coloring, adhesion modifiers, etc. It can also be made.

  The thickness of the adhesive layer is preferably 1 μm to 100 μm, more preferably 3 to 50 μm, and even more preferably 10 to 30 μm. If it is 1 micrometer or more, there exists a tendency for adhesiveness to improve and sufficient adhesive force is acquired. On the contrary, if the thickness is 100 μm or less, not only the transparency of the film is improved, but also after the window film is attached to the window glass, when peeled off, no cohesive failure occurs between the adhesive layers, and the adhesive remains on the glass surface. There is a tendency to disappear.

[Other functional layers]
The window film according to the present invention has a conductive layer, an antistatic layer, a gas barrier layer, an easy-adhesion layer (adhesive layer), and an antifouling layer between each layer and between the substrate and each layer for the purpose of adding further functions. Deodorant layer, droplet layer, slippery layer, wear-resistant layer, antireflection layer, electromagnetic wave shielding layer, ultraviolet absorbing layer, infrared absorbing layer, printed layer, fluorescent light emitting layer, hologram layer, release layer, high above You may have 1 or more of functional layers, such as infrared cut layers (metal layer, liquid crystal layer) other than a refractive index layer and a low-refractive-index layer, and a colored layer (visible light absorption layer).

[Film pasting substrate]
The window film of this embodiment is affixed to a base | substrate.

  The method of sticking to the substrate is not particularly limited, but since the effects of the present invention are remarkably exhibited, a method of sticking the window film to the wet glass surface, a so-called water sticking method may be used. preferable. That is, the method of attaching to the substrate includes a step of wetting the substrate with an aqueous medium, the window film of the above embodiment is disposed on the substrate, and the film surface opposite to the substrate is rubbed to rub the aqueous medium on the substrate. And a step of removing.

  The present invention also includes a step of wetting the substrate with an aqueous medium, a step of disposing the window film of the above-described embodiment on the substrate, and pressing the film surface opposite to the substrate to remove the aqueous medium on the substrate. There is also provided a method for producing a film pasting substrate.

  The aqueous medium used is not particularly limited, but is preferably water or a solution (or suspension) containing water and a surfactant. As the surfactant used, an anionic surfactant, a nonionic surfactant, an amphoteric surfactant, and the like can be used, and an anionic surfactant is more preferable.

  The content of the surfactant used in the aqueous medium is usually about 0.1 to 10% by mass with respect to 100% by mass of the aqueous medium.

  The method of wetting the substrate with the aqueous medium is not particularly limited, and examples thereof include a method of spraying the aqueous medium on the front surface of the application site using a sprayer or the like.

  A sticking position is determined while the aqueous medium remains on the substrate, and the film is placed on the substrate.

  The material of the member used when the film surface (film outermost layer) opposite to the substrate is rubbed is preferably rubber. For example, urethane, silicon, latex, isoprene rubber, butadiene rubber, chloroprene rubber, acrylic rubber More preferably, the rubber is composed of a combination thereof. Examples of the member include a squeegee and a roller.

  Since the obtained film has a dielectric multilayer film containing a resin, it is preferably used for application to an object to be applied (substrate) having a curved surface shape such as a window of a vehicle, for example, an automobile window. In the case of a substrate having such a curved shape, particularly a substrate having a curved shape with a radius of curvature of less than 2000 mm, the influence of the load at the time of bonding becomes larger, which is preferable in that the effects of the present invention are more easily obtained. In other words, a preferred embodiment of the present invention is a window film for attaching to a substrate having a curved shape with a radius of curvature of less than 2000 mm. The lower limit of the radius of curvature is not particularly limited, but is usually 50 mm or more from the viewpoint of moldability and the like.

  Although it does not restrict | limit especially as a base | substrate which is a sticking target object, It is preferable that it is glass. Examples of the glass include inorganic glass and organic glass. The inorganic glass is not particularly limited, and examples thereof include various types of inorganic glass such as float plate glass, polished plate glass, mold plate glass, netted plate glass, lined plate glass, heat ray absorbing plate glass, and colored plate glass.

  Examples of the organic glass include glass plates made of resins such as polycarbonates, polystyrenes, and polymethyl methacrylates. These organic glass plates may be a laminate formed by laminating a plurality of sheet-shaped ones made of the resin. Regarding the color, not only the transparent glass plate but also glass plates of various colors such as general-purpose green, brown and blue used for vehicles and the like can be used.

  The thickness of the glass is preferably about 1 to 10 mm in consideration of strength and infrared light transmittance in the visible light region.

  The effects of the present invention will be described using the following examples and comparative examples. Unless otherwise specified, each operation is performed at room temperature (25 ° C.). In addition, this invention is not limited to an Example below.

(Example 1)
(Formation of dielectric multilayer)
Polyethylene terephthalate (polyester (1)) and polyethylene naphthalate (polyester (2)) were melted at 250 ° C., and a layer formed of polyester (1) was formed from a 500-layer multi-layer extrusion die with a film thickness of 100 nm. The layer formed from the polyester (2) was pushed out to a film thickness of 150 nm. The film thus extruded was stretched approximately twice in length and approximately twice in width, and then heat-set and cooled to produce a dielectric multilayer film (thickness: 10 μm).

  The obtained dielectric multilayer film was thermocompression bonded onto a polyester film (trade name A4300, manufactured by Toyobo Co., Ltd., double-sided easy adhesion treatment, thickness 50 μm).

  Next, γ-aminopropyltrimethoxysilane was applied to the hard coating solution application surface of the dielectric multilayer film to a thickness of 3 μm on the hard coating solution application surface of the dielectric multilayer film to provide an easy adhesion layer.

(Formation of adhesive layer)
60 parts by mass of ethyl acetate and 20 parts by mass of toluene were mixed, and further 20 g of acrylic adhesive (Arontack M-300, manufactured by Toagosei Co., Ltd.) was added to prepare an adhesive layer coating solution. This coating solution was applied on the surface of the polyester film opposite to the dielectric multilayer film so that the film thickness was 25 μm after drying, and dried at 80 ° C. for 2 minutes to prepare an adhesive layer.

(Preparation of hard coat solution)
Acrylic hard coat liquid (Acryt 0403KA, manufactured by Taisei Fine Chemical Co., Ltd., solid content 30% by mass, MEK dilution) is diluted with MEK (solid content 20% by mass), and carnauba wax is mixed to obtain a hard coat liquid (hard coat liquid Carnauba wax content with respect to solid content 0.05 parts by mass).

(Preparation of window film)
On the dielectric multilayer film (on the easy adhesion layer), a hard coat solution was applied so that the film thickness was 5 μm after drying with a gravure coater. After drying at 100 ° C. for 1 minute to drive off the solvent, the film was cured by UV light irradiation to obtain a window film.

Example 2
In the preparation of the hard coat solution, a window film was prepared in the same manner as in Example 1 except that the carnauba wax was mixed to give a hard coat solution so that the carnauba wax content relative to the solid content of the hard coat solution was 0.1 parts by mass. Got.

Comparative Example 1
A window film was obtained in the same manner as in Example 1 except that no carnauba wax was added in the preparation of the hard coat solution of Example 1.

Comparative Example 2
In the preparation of the hard coat liquid of Example 1, instead of carnauba wax, a fluorine-based compound (2- (perfluorobutyl) was used so that the content relative to 100 parts by mass of the solid content in the hard coat liquid was 0.03 parts by mass. A window film was obtained in the same manner as in Example 1 except that ethyl acrylate) was added.

Comparative Example 3
In the preparation of the hard coat solution of Example 1, the same procedure as in Example 1 was conducted except that the carnauba wax was mixed to give a hard coat solution so that the carnauba wax content relative to the solid content of the hard coat solution was 3 parts by mass. A window film was obtained.

Example 3
(Preparation of hard coat solution)
0.55 parts by mass of a fluorine-based compound (2- (perfluorobutyl) ethyl acrylate) in 100 parts by mass of a polysiloxane-based hard coat (containing a silicone resin) (Surcoat BP-16N manufactured by Doken Co., Ltd., solid content: 20% by mass) After adding to obtain a polysiloxane hard coat solution, mix with 25 g of polysiloxane hard coat solution to 75 g of acrylic hard coat solution (0403KA, manufactured by Taisei Fine Chemical Co., Ltd., solid content 30% by mass, diluted MEK). It was set as the hard-coat liquid (0.5 mass part of fluorine-type compounds with respect to hard-coat liquid solid content).

(Preparation of window film)
The hard coat liquid was applied to the hard coat layer application surface of the film obtained in the column for forming the dielectric multilayer film of Example 1 so that the film thickness after drying was 5 μm with a gravure coater. It was dried at 100 ° C. for 2 minutes to drive off the solvent, and then cured by UV light irradiation to obtain a window film.

Example 4
In the preparation of the hard coat solution of Example 3, a fluorine compound (2- (perfluorobutyl) ethyl acrylate) was added so that the content of the fluorine compound was 1 part by mass with respect to the solid content of the hard coat solution. A window film was obtained in the same manner as in Example 3 except that.

Example 5
(Preparation of hard coat solution)
0.2 parts by weight of perfluorobutyl ethanol having a fluorine bond (perfluorobutylethyl group) is added to 500 parts by weight of a polysiloxane hard coat (Surcoat BP-16N, manufactured by Doken Co., Ltd., solid content 20% by mass), and added 0.05 parts by mass of LiCl was added as an agent and reacted at 0 ° C. for 2 hours to obtain a polymer liquid (fluorine bond (constituent unit of perfluorobutylethyl group) in the polymer was 0.2 parts by mass). Thereafter, 75 kg of acrylic hard coat liquid (0403KA, manufactured by Taisei Fine Chemical Co., Ltd., solid content of 30% by mass, diluted MEK) was mixed with 25 kg of polymer liquid to obtain a hard coat liquid (fluorine bond to hard coat liquid solid content). (Perfluorobutylethyl group structural unit) is 0.05 parts by mass).

(Preparation of window film)
The hard coat liquid was applied to the hard coat layer application surface of the film obtained in the column for forming the dielectric multilayer film of Example 1 so that the film thickness after drying was 5 μm with a gravure coater. It was dried at 100 ° C. for 2 minutes to drive off the solvent, and then cured by UV light irradiation to obtain a window film.

Example 6
In the preparation of the hard coat solution of Example 5, except that the hard coat solution was prepared so that the fluorine bond (constituent unit of perfluorobutylethyl group) was 0.5 parts by mass with respect to the solid content of the hard coat solution. A window film was obtained in the same manner as in Example 5.

Comparative Example 4
A window film was obtained in the same manner as in Comparative Example 1 except that the following dielectric multilayer film was formed.

(Formation of dielectric multilayer)
(Preparation of coating liquid L1 for forming a low refractive index layer)
22.5 parts by weight of colloidal silica (Snowtex OS, manufactured by Nissan Chemical Industries, solid content 20% by weight), 32.5 parts by weight of pure water, and a 1% by weight aqueous solution of a surfactant (Lapisol A30, manufactured by NOF Corporation) 1 After the addition of parts by weight, 280 parts by weight of a 5% by weight aqueous solution of alkali-treated gelatin (average molecular weight 130,000) was heated to 45 ° C., and 240 parts by weight of pure water was added with stirring and stirred for 10 minutes. A coating liquid L1 for forming a refractive index layer was prepared.

(Preparation of silica-attached titanium dioxide sol)
After adding 2 parts by weight of pure water to 0.5 parts by weight of 15.0% by weight titanium oxide sol (SRD-W, volume average particle size 5 nm, rutile type titanium dioxide particles, manufactured by Sakai Chemical Co., Ltd.), the mixture was heated to 90 ° C. . Next, 1.3 parts by weight of an aqueous silicic acid solution (sodium silicate 4 (manufactured by Nippon Kagaku Co., Ltd.) diluted with pure water so that the SiO ₂ concentration becomes 2.0% by weight) was gradually added. A heat treatment at 175 ° C. for 18 hours in an autoclave, cooling, and then concentrating on an ultrafiltration membrane to form a titanium dioxide sol having a solid content of 20% by weight of SiO ₂ attached to the surface (hereinafter silica adhesion) Titanium dioxide sol) was obtained.

(Preparation of coating liquid H1 for forming a high refractive index layer)
45 parts by weight of the silica-attached titanium dioxide sol (solid content 20.0% by weight), 10 parts by weight of a 5% by weight aqueous solution of a polyoxyalkylene dispersant (Marialim AKM-053, manufactured by NOF Corporation), 3% by weight boric acid After 10 parts by weight of an aqueous solution and 10 parts by weight of a 2% by weight citric acid aqueous solution were added in order, while heating to 45 ° C. and stirring, polyvinyl alcohol (JC-25, polymerization degree 2500, saponification degree 99.5 mol%, Japanese vinegar Bipoval Co., Ltd.) 5 wt% aqueous solution 20 parts by weight, surfactant (Lapisol A30, manufactured by NOF Corporation) 1 wt% aqueous solution 1 part by weight, pure water 4 parts by weight and high refractive index A layer forming coating solution H1 was prepared.

(Formation of dielectric multilayer)
Using a slide bead coating apparatus capable of 100-layer coating, a low refractive index layer forming coating solution L1 and a high refractive index layer forming coating solution H1 are heated to 45 ° C. and heated to 45 ° C. On the polyethylene terephthalate film (Toyobo A4300: double-sided easy-adhesion layer), the lowermost layer and the uppermost layer are L1, and other than that, H1 and L1 are alternated (that is, L1 / H1 / L1 / H1 /... / H1 / L1) A coating solution for forming a low refractive index layer and a coating solution for forming a high refractive index layer are supplied, and the film thickness upon drying is 300 nm for the lowermost layer, and 150 nm for the lower refractive index layers other than the lowermost layer. A total of 50 layers were simultaneously applied so that the refractive index layers were 150 nm each.

  Immediately after application, warm air of 80 ° C. was blown and dried to form a dielectric multilayer film consisting of 50 layers.

(Formation of adhesive layer)
60 parts by mass of ethyl acetate and 20 parts by mass of toluene were mixed, and further 20 g of acrylic adhesive (Arontack M-300, manufactured by Toagosei Co., Ltd.) was added to prepare an adhesive layer coating solution. This coating solution was applied on the surface of the polyester film opposite to the dielectric multilayer film so that the film thickness was 25 μm after drying, and dried at 80 ° C. for 2 minutes to prepare an adhesive layer.

Example 7
A window film was obtained in the same manner as in Example 1 except that the film described in the column for forming the dielectric multilayer film of Comparative Example 4 was used instead of the film described in the column for forming the dielectric multilayer film of Example 1. It was.

Example 8
A window film was obtained in the same manner as in Example 2 except that the film described in the column of dielectric multilayer film formation of Comparative Example 4 was used instead of the film described in the column of dielectric multilayer film formation of Example 1. It was.

Example 9
A window film was obtained in the same manner as in Example 3 except that the film described in the column for forming the dielectric multilayer film of Comparative Example 4 was used instead of the film described in the column for forming the dielectric multilayer film of Example 1. It was.

Example 10
A window film was obtained in the same manner as in Example 4 except that the film described in the column of dielectric multilayer film formation of Comparative Example 4 was used instead of the film described in the column of dielectric multilayer film formation of Example 1. It was.

Example 11
A window film was obtained in the same manner as in Example 5 except that the film described in the column of dielectric multilayer film formation of Comparative Example 4 was used instead of the film described in the column of dielectric multilayer film formation of Example 1. It was.

Example 12
A window film was obtained in the same manner as in Example 6 except that the film described in the column of dielectric multilayer film formation of Comparative Example 4 was used instead of the film described in the column of formation of dielectric multilayer film of Example 1. It was.

  Table 1 shows the coefficient of kinetic friction when wet for the window films obtained in the examples and comparative examples.

(Evaluation method 1: When the radius of curvature of the laminated glass is 2000 mm or more)
Wet the entire film application position of the glass film bonding surface with a radius of curvature of 10,000 mm with water and a surfactant (Emal 0 Kao) mixed solution (mixed with 3 g of surfactant in 100 g of water). The window film manufactured in the example is placed on the glass at the application position so that the adhesive layer is on the glass, and the outermost surface is rubbed with a rubber member (squeegee) having a rubber hardness of 60 made of urethane rubber. The infrared transmittance A (%) of the film-attached glass from which the mixed solution was removed was measured by the following method.

  Using a spectrophotometer (using an integrating sphere, manufactured by Hitachi, Ltd., U-4000 type), the transmittance of each film-attached glass in the region of 300 nm to 2000 nm was measured. As the infrared transmittance, the value of transmittance at 1200 nm was used.

  Separately, the infrared transmittance B (%) was measured in the same manner as described above for the window film before glass bonding.

  Infrared transmittance difference (%) before and after bonding = infrared transmittance A (%) − infrared transmittance B (%) was determined and evaluated according to the following evaluation criteria.

◎: Infrared transmittance difference (%) before and after bonding is less than 0.2% ○: Infrared transmittance difference (%) before and after bonding is 0.2% or more and less than 0.5% △: Before and after bonding Infrared transmittance difference (%) of 0.5% or more and less than 1% ×: Infrared transmittance difference (%) before and after bonding 1% or more and less than 5% XX: Infrared transmittance before and after bonding The difference (%) is 5% or more.

(Evaluation method 2: When the radius of curvature of the laminated glass is less than 2000 mm)
Evaluation was performed in the same manner as in Evaluation Method 1 except that glass having a radius of curvature of 1,000 mm was used as the substrate.

  The results are shown in Table 1.

  Even if the window films of Examples 1 to 12 were wet rubbed with a rubber member and bonded to glass, there was little decrease in infrared reflectivity, and the reflection characteristics inherent to the window film could be maintained. . Further, even when a substrate having a radius of curvature of less than 2,000 mm was used, there was little decrease in infrared reflectivity, and the inherent reflection characteristics of the window film could be maintained.

  On the other hand, the window films of Comparative Examples 1 to 4 had a large reduction in infrared reflectivity when they were rubbed with a rubber member in a wet state and bonded to glass, and the reflection characteristics inherent to the window film were reduced. In addition, when a substrate having a radius of curvature of less than 2,000 mm was used, the reduction in infrared reflectivity was more significant.

10 Window film,
11 outermost layer,
12 Dielectric multilayer film,
13 substrate,
14 Adhesive layer,
A Reverse side of the substrate bonding surface,
B Substrate bonding surface.

Claims (5)

Having a dielectric multilayer,
A window film characterized by having a wet dynamic friction coefficient of 0.2 to 0.5 between the reverse surface of the substrate bonding surface and an elastic body having a rubber hardness of 60.   The window film of Claim 1 stuck on the base | substrate which has a curved surface shape whose curvature radius is less than 2000 mm.   The window film according to claim 1, wherein the dielectric multilayer film includes at least one of a polyester-based polymer and a water-soluble polymer.   (1) to (3) in which the outermost layer facing the substrate bonding surface includes (1) a wax, (2) a silicone compound and a fluorine compound, and (3) a fluorine-containing silicone. The window film of any one of Claims 1-3 satisfy | fills at least one. Wetting the substrate with an aqueous medium;
Disposing the window film according to any one of claims 1 to 4 on the substrate, pressing the film surface opposite to the substrate, and removing the aqueous medium on the substrate;
The manufacturing method of the film sticking base | substrate which has these.